Stabilized acrylonitrile polymer composition and method of preparing same



United States Patent STABILIZED ACRYLONITRILE POLYMER COMPOSITION AND METHOD OF PRE- PARING SAME Richard R. Holmes, Bethesda, Md., and Lloyd T. Jenkins,

Decatur, Ala., assignors to The Chemstrand Corporation, Decatur, Ala., a corporation of Delaware N0 Drawing. Application May 23, 1956 Serial No. 586,675

20 Claims. (Cl. 260-29.6)

This invention relates to the stabilization of acrylonitrile polymers and blends thereof. More particularly, it relates to the stabilization of acrylonitrile polymers and blends thereof which have a tendency to develop color upon standing or application of heat.

The term polymer, as employed in the instant description and claims, is intended to include homopolymers, copolymers, and blends thereof, said polymers, con taining at least 80 percent by weight of polymerized or copolymerized acrylonitrile in the polymer molecule.

Acrylonitrile polymers containing 80 percent or more of acrylonitrile are generally insoluble in the more common solvents. And, in those instances where suitable solvents have been found, in order to effect solution, the application of heat is usually necessary. Where heat is employed to efiect solutions, from which shaped articles are to be formed, a tan to'dark brown color frequently develops in the solutions and therefore is carried over into the product formed therefrom. This color also develops in solutions upon standing for prolonged periods of time.

The mechanism which causes color formation has not been definitely ascertained, although a variety of reasons therefor have been advanced. The presence of metal ions, such as iron, copper and manganese in the solutions may cause the color. The employment of amide compounds as solvents may result in formation of amines when heat is applied and cause color in the compositions. Impurities present in the solvents have also been cited as a cause. Whatever may be the reason for color formation, it results in compositions and products of undesirable standards and therefore, has been the source of concern, particularly in commercial operations where such types ofpolymers or copolymers are employed.

Accordingly, it is an object of the present invention to prevent undesirable color formation in acrylonitrile polymer compositions.

Another object is to minimize color formation when solutions of the acrylonitrile polymers are permitted to stand for a prolonged period of time or upon application of heat.

It is also an object of the invention to prevent color formation in acrylonitrile polymers at elevated temperaturcs.

A still further object of the invention is the production of solutions of acrylonitrile polymers and articles produced therefrom having improved color characteristics.

- Otherobjectsand advantages will be apparent from a consideration of the description of the invention which follows hereafter.

In general, the objects of the invention are accom I plished bydissolving the polymer of acrylonitrile in a suitable solvent therefor and preventing or minimizing color formation by the presence in the solution as an inhibiting agent, ,a combined reagent comprising various mixtures of glycolic acid, ethylene diamine tetra-acetic acid and the sodium salt and sodium acid salts thereof, and'an inor;

.N-vinylsuccinimide; methylenemalonic esters; itaconic 2,878,200 Patented Mar. 17, i959 ganic acid having an ionization constant greater than 1 X 10*.

The components of the inhibiting agent may be employed in equal or unequal amounts, any one constituent being present in a range of from 98 to 1 percent in a three component system and 99 to 1 percent in a two component system. The total amount of inhibiting agent may be employed in a range of about 0.3 to 15 percent, based on the total polymer weight. However, it is pre ferred that the inhibiting agent of the instant invention be present in a small amount compared to the amount of polymer dissolved. Thus, although the amount is not critical, it is preferred that the inhibiting agent be present in the amount of about 0.3 to 3 percent, based on the total weight of the polymer. The inhibiting agent may be added to the solvents before or after the polymer is dissolved therein. The inhibiting agent permits exposure to high temperatures for prolonged standing periods without the development of the objectionable color which usually results in such solutions. The compositions of the instant invention may be prepared in a varying temperature range. For example, the compositions of the instant invention may be prepared by mixing the polymer, a suitable solvent and the inhibiting agent at any temperature or heating the mixture to a temperature up to the boiling point of the solvent.

Among the acids having an ionization constantgreater than 1X10 which may be employed in practising the instant invention are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, etc.

Among the solvents which may be used in practising the instant invention are N,N-dimethylformamide, N,N- dimethylacetamide, aqueous zinc chlorideysulfflric acid, aqueous nitric acid, aqueous sodium thiocyanate, ethylene carbonate, sulfolane, nitromethane, etc. 3 i

The polymeric materials, which may be employed in the practice of the present invention, are polyacrylonitrile, copolymers, including binary and ternary polymers containing at least percent by weight of acrylonitrile in the polymer molecule, or a blend comprising polyacrylonitrile or copolymers comprising acrylonitrile with from 2 to 50 percent of another polymeric material, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight. While thepreferred polymers least 80 percent of acrylonitrile, generally recognized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent acrylonitrile and the same stability is realized with the inhibiting agents defined herein. The acrylonitrile polymers containing less than 80 percent acrylonitrile are useful in forming films, coating compositions, molding operations, lacquers, etc.,

color is extremely important. a

For example, the polymer may be a copolymer of from 80 to 98 percent acrylonitrile and from 2 to 20 percent of another monomer containing the C=C linkage and copolymerizable with acrylonitrile. Suitable mono-olefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids; the acrylates, such as methylmethacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl metbacrylate, beta-chloroethyl methacrylate, and the correspondingesters of acrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, 1-chloro-1-bromo-ethylene;- methacrylonitrile; acrylamide and methacrylamide; alpha-chloroacrylamide, or monoalkyl substitutionproducts thereof; methyl vinyl ketone; vinyl carboxylates, such as vinyl acetate, vinyl chloroacetate, vinyl propionate, and vinyl stearate; N-vinylimides, such as N-vinylphthalimide and in all of which applications the alleviation of undesirable as'reeoo acid and itaconi r; N- ylc az v yl n alkyl vinyl esters; vinyl sulfonic acid; ethylene alpha, betadicarboxylic acids or their anhydrides or derivatives, such as diethylcitraconate, diethylmesaconate, styrene, vinyl naphthalene; vinyl-substituted tertiary hcterocyclic amines, such as the vinylpyridines and alkyl-substituted vinylpyridines, for example, 2-vinylpyridine, 4-vinylpyridine, 2- methyl-S-vinylpyridine, etc.; l-vinylimidazole and alkylsubstituted l-vinylimidazoles, such as 2-, 4-, or S-methyl- 1.-vinylimidazole, and other C=C containing polymerizable, materials.

The polymer may be a ternary interpolymer,- for example, products obtained hy the interpolymerization of acrylonitrile and two or more of any of the monomers, other than acrylonitrile, enumerated above. More specifically, and preferably, the ternary polymer comprises acrylonitrile, methacrylonitrile, and 2-vinylpyridine. The ternary polymers preferably contain from 80 to 97 percent of acrylonitrile, from 1 to percent of a vinylpyridine or a l-vinylimidazole, and from 1 to 18 percent of another substance, such as methacrylonitrile or vinyl chloride.

The polymer may also be a blend of a polyacrylonitrile or of a binary interpolymer of from 80 to 99 percent acrylonitrile and from 1 to 20 percent of at least one other C=C containing substance with from 2 to 50 percent of the weight of the blend of a copolymer of from 10 to 70 percent of acrylonitrile and from 30 to 90 percent of at least one other (hC containing polymerizable monomer. Preferably, when the polymeric material comprises a blend, it will be a blend of a co- Polymer of 90 to 98 percent acrylonitrile and from 2 to 10 percent of another mono-olefinic monomer, such as vinyl acetate, which is not receptive to dyestuff, with a sufficient amount of a copolymer of from 10 to 70 percent of acrylonitrile and from 30 to 90 percent of a vinylsubstituted tertiary heterocyclic amine, such as vinylpyridine or l-vinylimidazole, to give a dyeable blend having an overall vinyl-substituted tertiary heteroyclic amine content of from 2 to 10 percent, based on the weight of the bl n The polymers, useful in the practice of the present invention, may be prepared by any conventional polymerization procedures, such as mass polymerization methods, solution polymerization methods, or aqueous emulsion procedures. However, the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the fiber fabrication operations. The preferred suspension polymerization may utilize batch procedures, wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents. A more desirable method involves the semi-continuous procedure in which the polymerization reactor containing the aqueous medium is charged with the desired monomers and the continuous withdrawal of polymer may also be emplaye The polymerization is catalyzed by means of any watersoluble peroxy compound, for example the potassium, ammonium and other water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and any other water-soluble compound containing a peroxy group (.'O--O). A wide variation in the quantity of peroxy compound is possible. For example, from 0.1 to 3.0 percent by weight of the polymerizable monomer may he used. The catalyst may be charged at the outset of the reaction, or it may be added continuously or in increments throughout the reaction for the purpose of maintaining a more uniform concentration of catalyst in the reaction mass. The latter method is preferred because it tends to make the resultant polymer more uniform in its chemical and physical properties.

Although theuniform distribution of the reactants throughout the reaction mass can be achieved by vigdrophilic radicals.

or g tion, it is g nera y d sir bl o promote the uniform distribution of reagents by using inert wetting agents, or emulsion stabilizers. Suitable reagents for this purpose are the water-soluble salts of fatty acids, such as sodium oleate and potassium stearate, mixtures of water-soluble fatty acid salts, such as common soaps prepared by the saponification of animal and vegetable oils, the amino soaps, such as salts of triethanolamine and dodecylmethylamine, salts of rosin acids and mixtures thereof, the water-soluble salts of half esters of sulfuric acid and long chain aliphatic alcohols, sulfonated hydrocarbons, such as alkyl aryl sulfonates, and any other of a wide variety of Wetting agents, which are in general organic compounds containing both hydrophobic and hy- The quantity of emulsifying agents will depend upon the particular agents selected, the ratio of monomer to be used, and the conditions of polymerization. In general, however, from 0.01 to 1.0 percent by weight of the monomers may be employed.

The emulsion polymerizations are preferably conducted in glass or glass-lined vessels which are provided with a means for agitating the contents. Generally, rotary stirring devices are the most effective means of insuring the intimate contact of the reagents, but other methods may be successfully employed, for example by rocking or tumbling the reactors. The polymerization equipment generally used is conventional in the art and the adaptation of a particular type of apparatus to the reaction con templated is within the province ofone skilled in the art. The articles manufactured therefrom may be produced by well-known conventional methods, for example, the wet-spinning, dry-spinning and melt-spinning methods for producing fibers.

The following examples are illustrative rather than limitative and all parts, proportions and percentages are by weight unless otherwise specified.

EXAMPLE I 7.5 grams of a polymer blend of 88 percent of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate and 12 percent of a copolymer of 50 percent of acrylonitrile and 50 percent of 2-methyl-5 vinyl pyridine were added to 45 milliliters of N,N-dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated to 70 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a con trol. The purity is set forth below. Subsequently, like samples were prepared but with 0.225 gram of a color inhibitor containing 0.075 gram each of glycolic acid, ethylene diamine tetra-acetic acid and sulfuric acid; 0.150 gram of a color inhibitor containing 0.075 gram each of glycolic acid and sulfuric acid; and 0.150 gram of a color inhibitor containing 0.075 gram each of ethyiene diamine tetra-acetic acid and sulfuric acid. The purity is set forth below.

7.5 grams of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate were added to 45 milliliters of N,N-dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated for 35 minutes at 70 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity is set forth below. Subsequently, like samples were prepared but with 0.225 gramofa color inhibitor containing 0.075 gram each of glycolic acid, ethylene diamine tetra-acetic acid and sulfuric acid; 0.150 gram of a color inhibitor containing 0.075 gram each of glycolic acid and sulfuric acid; and 0.150 gram of a color inhibitor containing 0.075 gram each of ethylene diamine Betta-acetic acid and sulfuric acid. The purity is set forth elow.

Table II Inhibitor Percentage Purity Used Control 10.2 Glycolic Acid, Ethylene. Dlamine Acetic Acid and Sulfuric Acid 3 4. 3 Glycolic Acid and Sulfuric Acid 8. 7

Ethylene Diamine Tetra-Acetic Acid and Sulfuric Acid 2 4. 7

EXAMPLE n 7.5 grams of an acrylonitrile homopolymer were added to 45 milliliters of N,N-dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated for 50 minutes at 90 C." It was then quickly cooled to room temperature and the color measured. This sample was used asacontrol; of the control sample is set forth below. Subsequently, like samples were prepared but with 0.225 gram of a-color inhibitor containing 0.075 gram each of glycolic acid, ethylene diamine tetra-acetic acid and sulfuric acid; 0.150 gram of a color inhibitor containing 0.075 gram'each of glycolic acid and sulfuric acid; and 0.150 gram of a color inhibitor containing 0.075 gram each of ethylene diamine tetra-acetic acid andsulfuric acid. The purity is set forth below.

Table III Inhlbitor Fercen tage Purity Used " Oontro1 t as Glycolic; Acid, Ethylene Diamine Tetra- Acetic-Acid and Sulfuric Acid... .1 t 3 5.5 Glycelic Acid and Sulfuric Acid 2 5. 5 Ethylene Dlamine Tetra-Acetic Acid and Sulfuric Acid 2 3 The sodium salt and sodium acid salts of ethylene diamine tetra-acetic acid when employed in practising the present invention will give the same results as ethylene diamine tetra-acetic acid with respect to the purity readings as set forth above.

The tests for color indicative of approaching whiteness used throughout the examples consist of measurements of purity as calculated from the tristimulus values determined on a General Electric spectrophotometer by the methods recommended by the Standard Observer and Coordinate System of the International Commission on Illumination, as fully set forth in the Handbook of Colorimetry pub lished by The Technology Press, Massachusetts Institute of Technology in 1936.

The compositions of the instant invention present many advantages. For example, products formed from the polymer solutions of the instant invention are free of objectionable color and therefore of greater commercial value. In preparing the polymer solutions, heat may be applied without the danger of color formation and the solutions,

. if necessary, may stand for prolonged periods and remain free of color. The inhibiting agents are readily available and inexpensive. Therefore, no great increase in production cost is necessary. The compositions containing the inhibitors may be prepared without going through detailed and elaborate procedures that necessitate expensive changes in the design of the apparatus used to manufacture them.

It will be understood to those skilled in the art that many apparently widely different embodiments of this wherein the polymer is a copolymer containing from 80 inventionean be made ,without departing from the spirit and scope thereof. Accordingly, it is tobe understood that this invention is notto be limited to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. Anew composition of matter comprising a polymer containing at least 80% of acrylonitrile, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of an inorganic acid having an ionization constant greater than 1X10 and a compound selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid, mixtures of glycolic acid and ethylene diamine tetraacetic acid, and mixtures of glycolic acid and the sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid..

, ,2. A new composition'of matter as defined in claim 1 to .98 percent ,of,acrylonitri le and from 2 to percent of another polymerizable mono-olefinic monomer copolymerizable therewith.

v The'purity 3. A new composition of t'natter as defined in claim 1 wherein the polymer is a blend of 80m 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile I and 2 to 10 percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-vinyl pyridine.

4. A new composition of matter as defined in claim 1 wherein the polymer is .polyacrylonitrile.

5. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains glycolic acid, ethylene diamine tetra-acetic acid and sulfuric acid.

6. A new composition of matter as defined in claim 1 wherein the inhibiting 'agent contains glycolic acid and sulfuric acid. a t

7. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains ethylene diamine tetra-acetic acid and sulfuric acid.

' 8. A'new composition ofmatter as defined in claim 1 wherein the inhibiting agent contains the sodium salt of ethylene diamine tetra-acetic acid and sulfuric acid.

9. A new composition of matter as defined in claim 1 wherein the inhibiting agent contains the disodium acid salt of ethylene diamine tetraacetic acid and sulfuric acid.

10. A new composition of matter comprising a polymer blend of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to 10 percent of another polymerizable mono-olefinic monomer and (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of a vinyl substituted tertiary heterocyclic amine, said blend having an overall vinyl substituted tertiary heterocyclic amine content of from 2 to 10 percent based on the weight of the blend, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of an inorganic acid having an ionization constant greater than 1X10 and a substance selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and sodium acid salts of ethylene diamine tetraacetic acid, mixtures of glycolic acid and ethylene diamine tetra-acetic acid, and mixtures of glycolic acid and the sodium salt and sodium acid salts of ethylene diamine tetra-acetic acid.

11. A new composition of matter comprising a polymer containing at least of acrylonitrile, a solvent therefor, and 0.3 to 15%, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of an inorganic acid having an ionization constant greater than 1X10 and a compound selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid, mixtures of glycolic acid and ethylene diamine tetraacetic acid, and mixtures of glycolic acid and the o i m salt n the sodium a sa ts o thy ene diamine tetraacetic acid,

12. A method for preparing a new composition of matter comprising mixing a polymer containing at least 80% of acrylonitrile and up to 20% of another monoolefinic monomer copolymerizable therewith with a solvent therefor, and an inhibiting agent containing substantially equal proportions based by weight of an inorganic acid having an ionization concentrate greater than 1X10" and a compound selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and sodium acid salts of ethylene diamine tetraacetic acid, mixtures ofglycolic acid and ethylene diamine tetraacetic acid, and mixtures of glycolic acid and sodium salt and the sodium acidsalts of ethylene diamine tetraacetic acid; and heating the mixture to form a homogeneous solution.

13. The method as defined in claim 12 wherein the polymer is a copolymer containing from 80 to 98 percent of acrylonitrile and from 2 to 20 percent of another polymerizable mono-olefinic monomer coplymerizable therewith.

14. The method as defined in claim 12 wherein the polymer is a blend of 80 to 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to percent of vinyl acetate and 1 to percent of (B') a copolymer containing 1.0 to 70 percent of acrylonitrile and to 90 percent of 2-methyl-5-vinyl pyridine.

15. The method as defined in claim 12 wherein the polymer is polyacrylonitrile.

16. A method for preparing a new composition of matter as defined in claim "12 wherein the inhibiting agent contains glycolic acid, ethylene diamine tetra-acetic acid and sulfuric acid.

. 17. A method for preparing a new composition of matter as defined in claim 12 wherein the inhibiting agent contains glycolic acid and sulfuric acid.

18. A method for preparing a new composition of matter as defined in claim 12 wherein the inhibiting agent contains ethylene diamine tetraacetic acid and sulfuric acid.

1. A me h d for p ep ing a n c mpqsitiqn of matter comprising mixing a copolymer containing to 98 percent of acrylonitrile and 2 to 20 percent of vinyl acetate, with a solvent therefor, and 0.3 to 15%, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal'pror portions by weight of sulfuric acid and a compound selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid, mixtures of glycolic acid and ethylene diamine tetraacetic acid, and mixtures of glycolic acid and the sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid; and heating the mixture to a temperature in the range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

20. A method for preparing a new composition of matter comprising mixing a polymer blend of 80 to 99 percent of (A) a copolymer containing to 98 percent of acrylonitrile and 2 to 10 percent of vinylacetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of Z-methyl- S-vinylpyridine, with a solvent therefor, and 0.3 to 15 based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of sulfuric acid and a compound selected from the group consisting of glycolic acid, ethylene diamine tetraacetic acid, the sodium salt and sodium acid salts of ethylene diamine tetraacetic acid, mixtures of glycolic acid and ethylene diamine tetraacetic acid, and mixtures of glycolic acid and sodium salt and the sodium acid salts of ethylene diamine tetraacetic acid;

and heating the mixture to a temperature in the range of 25 C. to the boiling point of the mixture to form a homogeneous solution.

References Cited in the tile of this patent UNITED STATES PATENTS 

1. A NEW COMPOSITION OF MATTER COMPRISING A POLYMER CONTAINING AT LEAST 80% OF ACRYLONITRILE, A SOLVENT THEREFOR, AND AN INHIBITING AGENT CONTAINING SUBSTANTIALLY EQUAL PROPORTIONS BY WEIGHT OF AN INORGANIC ACID HAVING AN IONIZATION CONSTANT GREATER THAN 1X10-4 AND A COMPOUND SELECTED FROM THE GROUP CONSISTING OF GLYCOLIC ACID. ETHYLENE DIAMINE TETRAACETIC ACID, THE SODIUM SALT AND THE SODIUM ACID SALTS OF ETHYLENE DIAMINE TETRAACETIC ACID, MIXTURES OF GLYCOLIC ACID AND ETHYLENE DIAMINE TETRAACETIC ACID, AND MIXTURES OF GLYCOLIC ACID AND THE SODIUM SALT AND THE SODIUM ACID SALTS OF ETHYLENE DIAMINE TETRAACETIC ACID. 